WO2013094686A1 - 静電塗装用樹脂成形体 - Google Patents
静電塗装用樹脂成形体 Download PDFInfo
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- WO2013094686A1 WO2013094686A1 PCT/JP2012/083077 JP2012083077W WO2013094686A1 WO 2013094686 A1 WO2013094686 A1 WO 2013094686A1 JP 2012083077 W JP2012083077 W JP 2012083077W WO 2013094686 A1 WO2013094686 A1 WO 2013094686A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/007—Processes for applying liquids or other fluent materials using an electrostatic field
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
- B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/88—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised primarily by possessing specific properties, e.g. electrically conductive or locally reinforced
- B29C70/882—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised primarily by possessing specific properties, e.g. electrically conductive or locally reinforced partly or totally electrically conductive, e.g. for EMI shielding
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/16—Fillers
- B29K2105/165—Hollow fillers, e.g. microballoons or expanded particles
- B29K2105/167—Nanotubes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Definitions
- the present invention relates to a resin molded body for electrostatic coating.
- a molded body made of a thermoplastic resin is widely used in the industrial parts field mainly by injection molding. It is known that these molded bodies are coated on the surface in order to compensate for defects such as imparting design properties, imparting weather resistance to base resin, imparting impact resistance, imparting scratch resistance, and the like.
- electrostatic coating is a method in which electricity is applied to a thermoplastic resin molding that has been imparted with conductivity and sprayed with a paint with the opposite charge. Has been done. This is to improve the adhesion rate of the paint by utilizing the property of attracting each other by imparting opposite charges to the surface of the molded article and the paint.
- a conductive primer is applied to make the surface conductive in advance, as described in Patent Document 1, before applying the top coat to increase the coating efficiency. It is common to leave.
- thermoplastic resin by adding carbon-based fillers such as carbon black, acetylene black, and ketjen black, and metal-based fillers such as metal powder, etc. to the thermoplastic resin, conductivity or thermal conductivity is imparted to the insulating resin. It is known.
- Patent Document 2 proposes to impart surface conductivity to a molded body by kneading a conductive filler into an insulating thermoplastic resin as one method of surface conductivity.
- Patent Documents 3 to 6 disclose the use of carbon nanotubes as the conductive filler.
- JP 2006-045384 A International Publication No. 2004/050763 Pamphlet International Publication No. 00/68299 pamphlet JP 2004-143239 A JP 2009-280825 A JP 2010-043265 A
- a resin molded body for electrostatic coating having a surface resistance value of 9.9 ⁇ 10 13 ⁇ / ⁇ or less and a volume resistance value of 9.9 ⁇ 10 5 ⁇ ⁇ cm or less.
- the resin molded body for electrostatic coating according to (1) which is not more than cm.
- the thermoplastic resin is ABS resin, AES resin, ASA resin, AS resin, HIPS resin, styrene / acrylonitrile copolymer, polyethylene, polypropylene, polycarbonate (PC), polycarbonate and ABS alloy (PC / ABS), polyphenylene
- a charged paint is sprayed onto a resin molded body for electrostatic coating having a surface resistance value of 9.9 ⁇ 10 13 ⁇ / ⁇ or less and a volume resistance value of 9.9 ⁇ 10 5 ⁇ ⁇ cm or less.
- a charged paint is sprayed onto a resin molded body for electrostatic coating having a surface resistance value of 9.9 ⁇ 10 13 ⁇ / ⁇ or less and a volume resistance value of 9.9 ⁇ 10 5 ⁇ ⁇ cm or less.
- the manufacturing method of the resin molding which has a coating film made (10) A charged paint is sprayed onto a resin molded body for electrostatic coating having a surface resistance value of 9.9 ⁇ 10 13 ⁇ / ⁇ or less and a volume resistance value of 9.9 ⁇ 10 5 ⁇ ⁇ cm or less. A method for producing a vehicle part having a coating film.
- a resin molded body for electrostatic coating that is excellent in coating efficiency by electrostatic coating and excellent in mechanical properties.
- Resin molded body for electrostatic coating It is known that when a resin is molded, non-uniformity occurs in the surface and the center.
- a thermoplastic resin molding can be obtained by filling a resin melted by heat into a low-temperature mold cavity and cooling and solidifying, but in this case, a layer having a different resin flow can be formed due to a difference in cooling rate.
- a skin layer and a core layer are formed in a direction perpendicular to the flow.
- the skin layer refers to a thickness of about 200 ⁇ m in the thickness direction from the surface of the obtained molded body
- the core layer refers to a portion having a depth of about 200 ⁇ m or more.
- the orientation of the filler in the skin layer and the core layer is different, so that the conductive characteristics are different in each layer. Therefore, even if only the surface resistance value of the resin molding is controlled, the coating efficiency and mechanical characteristics in the actual electrostatic coating process cannot be controlled. Furthermore, even if only the volume resistance value of the resin molding is controlled, the coating efficiency and mechanical characteristics in the actual electrostatic coating process cannot be controlled. For example, in order to reduce the surface resistance value of a resin molded body to a resistance value capable of electrostatic coating (for example, 10 4 to 10 5 ⁇ / ⁇ ), it is necessary to add many conductive carbon fibers. Mechanical properties are degraded.
- a predetermined resistance value range is required for both the skin layer and the core layer. Adjust to.
- both skin layer and core layer require resistance values below a certain level. It is.
- the resin molded product has a surface resistance of 1.0 ⁇ 10 3 ⁇ / ⁇ or more and 9.9 ⁇ 10 13 ⁇ / ⁇ or less, and a volume resistance of 1.0 ⁇ 10 3 ⁇ ⁇ cm. As mentioned above, it controls to 9.9 * 10 ⁇ 5 > ohm * cm or less.
- the lower limit value of the surface resistance is more preferably 1.0 ⁇ 10 8 ⁇ / ⁇
- the lower limit value of the more preferable surface resistance is 1.0 ⁇ 10 10 ⁇ / ⁇
- the upper limit value of the more preferable surface resistance is 1.0 ⁇ . 10 12 ⁇ / ⁇ .
- a more preferable upper limit value of the volume resistance is 1.0 ⁇ 10 5 ⁇ ⁇ cm.
- the surface resistance value In order to make the surface resistance value less than 1.0 ⁇ 10 3 ⁇ / ⁇ , a large amount of conductive filler must be contained, which is not economical, and the matrix resin is liable to deteriorate. When the surface resistance value exceeds 10 14 ⁇ / ⁇ , the coating efficiency tends to be low.
- the resin molding for electrostatic coating having such a resistance value is excellent in coating efficiency even if either the surface resistance value or the volume resistance value is higher than the conventional value.
- favorable coating efficiency can be expressed by setting volume resistance to a predetermined range. Therefore, it is possible to reduce the amount of the conductive filler to be added, and thus it is possible to suppress a decrease in mechanical properties of the molded body. Even if the volume resistance value is within a predetermined range, if the surface resistance value is too large, the coating efficiency is lowered.
- surface resistance and volume resistance can be measured by the method as described in an Example.
- the resin used in the present invention is not particularly limited, but it is preferable to use a resin having high impact characteristics and fluidity.
- the resin having high impact characteristics include a thermoplastic resin having an IZOD impact strength of 200 J / m or more.
- Resins with high flow characteristics include melt flow rates of 10-30 g / 10 min.
- a thermoplastic resin that is (220 ° C., 10 kgf load) can be used.
- Styrene (co) polymers such as polystyrene, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, (meth) acrylic acid ester-styrene copolymer; Rubber reinforced resins such as ABS (acrylonitrile-butadiene-styrene) resin, AES (acrylonitrile-ethylene (EPDM) -styrene) resin, ASA (acrylonitrile-styrene-acrylate) resin, HIPS (impact polystyrene) resin; ⁇ -olefin (co) polymers containing at least one ⁇ -olefin having 2 to 10 carbon atoms as a monomer, such as polyethylene, polypropylene, and ethylene-propylene copolymer, and modified polymers thereof (chlorinated polyethylene, etc.), And olefin resins such as cyclic olefin copolymers; Eth
- ABS resin AES resin
- ASA resin AS resin
- HIPS resin styrene-acrylonitrile copolymer
- polyethylene polypropylene
- PC polycarbonate
- PC / ABS polycarbonate and ABS alloy
- PPE polyphenylene ether
- PA polyamide
- a resin obtained by adding other elastomer or rubber component to the above thermoplastic resin may be used.
- elastomers used for improving impact resistance include olefin elastomers such as EPR and EPDM, styrene elastomers such as SBR made of a copolymer of styrene and butadiene, silicon elastomers, nitrile elastomers, and butadiene elastomers.
- Elastomers urethane elastomers, polyamide elastomers, ester elastomers, fluoroelastomers, natural rubber, and modified products in which reactive sites (double bonds, carboxylic anhydride groups, etc.) are introduced into these elastomers are used Is done.
- Carbon fiber Although the carbon material added to resin is not specifically limited, for example, carbon fiber can be used.
- carbon fiber pitch-based carbon fibers, PAN-based carbon fibers, carbon fibers, carbon nanofibers, carbon nanotubes, and the like can be used. From the viewpoint of reducing the addition amount, it is preferable to use carbon nanotubes.
- the carbon nanotube of a preferred embodiment is a tube having a cavity at the center of the fiber, and the graphene surface extends substantially parallel to the fiber axis. In the present invention, “substantially parallel” means that the inclination of the graphene layer with respect to the fiber axis is within about ⁇ 15 degrees.
- the hollow portion may be continuous in the fiber longitudinal direction or may be discontinuous.
- the carbon fiber added to the resin has a higher conductivity imparting effect when the fiber diameter is narrower.
- the average fiber diameter is preferably 1 nm to 150 nm, more preferably 1 nm to 50 nm, and particularly preferably 1 nm to 20 nm. From the viewpoint of dispersibility, the average fiber diameter is preferably 2 nm or more, and more preferably 4 nm or more. Therefore, when considering the dispersibility and conductivity imparting effect, the average fiber diameter is preferably 2 to 20 nm, and most preferably 4 to 20 nm.
- the ratio (d 0 / d) between the fiber diameter d and the cavity inner diameter d 0 is not particularly limited, but is preferably 0.1 to 0.9, and more preferably 0.3 to 0.9.
- the lower limit of the BET specific surface area of the carbon fiber is preferably 20 m 2 / g, more preferably 30 m 2 / g, still more preferably 40 m 2 / g, and particularly preferably 50 m 2 / g.
- the upper limit of the specific surface area is not particularly limited, but is preferably 400 m 2 / g, more preferably 350 m 2 / g, still more preferably 300 m 2 / g, particularly preferably 280 m 2 / g, and most preferably 260 m 2 / g. .
- Various methods have been proposed for evaluating the surface crystal structure of carbon fibers. For example, there is a method using Raman spectroscopy. Specifically, the intensity ratio I D / peak intensity (I D ) in the range of 1300 to 1400 cm ⁇ 1 and peak intensity (I G ) in the range of 1580 to 1620 cm ⁇ 1 measured by Raman spectroscopy spectrum.
- a method of evaluating by I G (R value) is known.
- the R value of the carbon fiber is preferably 0.1 or more, more preferably 0.2 to 2.0, and further preferably 0.5 to 1.5. In addition, it shows that crystallinity is so low that R value is large.
- the consolidation specific resistance value of the carbon fiber is preferably 1.0 ⁇ 10 ⁇ 2 ⁇ ⁇ cm or less, and 1.0 ⁇ 10 ⁇ 3 ⁇ ⁇ cm to 9.9 ⁇ 10 ⁇ 3 at a density of 1.0 g / cm 3 . More preferably, ⁇ ⁇ cm.
- the fiber length of the carbon fiber is not particularly limited, but if the fiber length is too short, the conductivity imparting effect tends to be small, and if the fiber length is too long, dispersibility in the matrix resin tends to be difficult.
- the preferred fiber length is usually 0.5 ⁇ m to 100 ⁇ m, preferably 0.5 ⁇ m to 10 ⁇ m, and more preferably 0.5 ⁇ m to 5 ⁇ m, although it depends on the thickness of the fiber.
- the carbon fiber itself may be straight or may be curved and twisted.
- twisted and curved fibers are more preferable because they have excellent adhesion to the resin and have higher interfacial strength than linear fibers, so that deterioration in mechanical properties when added to a resin composite can be suppressed.
- this twisted structure even when dispersed in a small amount in the resin, it is a cause that the network between the fibers is not interrupted, and conductivity is not expressed in the fiber near the straight line as in the prior art It is more preferable in that conductivity is exhibited even in a low addition amount region.
- the amount of carbon fiber used in the resin molded body is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the resin. By using the preferable carbon fiber, it is possible to make the addition amount lower. A more preferable addition amount is 0.5 to 5 parts by mass. When the addition amount is less than 0.5 parts by mass, it is difficult to form a sufficiently conductive and thermally conductive path in the resin molded body. On the other hand, when the addition amount exceeds 10 parts by mass, the characteristics of the resin itself are easily lost.
- the breaking rate of the carbon fiber is preferably suppressed to 20% or less, more preferably 15% or less, and particularly preferably 10% or less.
- the breaking rate is evaluated by comparing the aspect ratios of carbon fibers before and after mixing and kneading (for example, measured by observation with an electron microscope SEM).
- the following method can be used.
- an inorganic filler when melt-kneaded into a thermoplastic resin or a thermosetting resin, high shear is applied to the aggregated filler, the filler is crushed and refined, and the filler is uniformly dispersed in the molten resin. If the shear during kneading is weak, the filler is not sufficiently dispersed in the molten resin, and a resin composite material having the expected performance and function cannot be obtained.
- a kneading machine that generates a high shearing force a machine using a stone mortar mechanism or a machine in which a kneading disk with high shear is introduced into a screw element using a twin screw extruder is used.
- a device that reduces shear by a co-directional twin-screw extruder that does not use a kneading disk or does not apply high shear such as a pressure kneader Therefore, it is desirable to perform kneading over time or kneading using a special mixing element in a single screw extruder.
- the kneading disk can be used in consideration of the dispersibility of the carbon fibers in the same-direction twin-screw extruder.
- a kneading disc can be used.
- Conditions such as temperature, discharge amount, and kneading time for melt kneading should be appropriately selected and determined according to the type and capacity of the kneading equipment and the properties and ratios of the components constituting the resin molded body for electrostatic coating. Can do.
- Molding method When manufacturing a molded article from these compositions, it can be based on the molding method of the resin composition known conventionally.
- the molding method include an injection molding method, a hollow molding method, an extrusion molding method, a sheet molding method, a thermoforming method, a rotational molding method, a laminate molding method, and a transfer molding method.
- the injection molding method is preferable.
- the molding temperature is set to be higher than the temperature used for normal thermoplastic resin injection molding. Specifically, injection molding is performed at a temperature 10 to 60 ° C. higher than the injection molding temperature recommended for the resin used.
- the recommended molding temperature of the resin indicated by the supplier is 220-230 ° C, but in a preferred embodiment of the present invention, the injection molding is preferably 230 ° C-290 ° C, more Preferably, it is carried out at 240 ° C to 270 ° C.
- the injection molding temperature is low, a shearing force is likely to be generated in the molten resin at the time of injection. In particular, an excessive shearing force is generated in the skin layer, the carbon fibers are oriented in the flow direction of the resin, and the resistance value is increased.
- the injection speed is preferably low, and the injection speed is the lowest speed that does not impair the surface appearance and dimensional accuracy of the molded product.
- an excessive shearing force is likely to be generated in the molten resin, particularly an excessive shearing force is generated in the skin layer, and the carbon fibers are oriented in the flow direction of the resin and the resistance value is increased.
- the resin molded body for electrostatic coating described above is used for products and parts that require coating with impact resistance, such as parts used in OA equipment, electronic equipment, and automotive parts such as automobile parts. It can be suitably used for painting.
- Thermoplastic resin ABS resin (Toyolac 100-MPM manufactured by Toray Industries, Inc., melt flow rate (220 ° C., 10 kgf load): 15 g / 10 minutes), Carbon nanotube: VGCF (registered trademark) -X manufactured by Showa Denko KK, average fiber diameter 15 nm, average fiber length 3 ⁇ m, BET specific surface area 260 m 2 / g.
- MFR Melt flow rate
- Reference example 1 100 parts by weight of ABS resin and 1 part by weight of carbon nanotubes are fed from the main feed port of the same-direction twin-screw extruder (TEX30 ⁇ manufactured by Nippon Steel Works), and the kneaded resin composition is cut into pellets by a pelletizer. processed.
- TEX30 ⁇ manufactured by Nippon Steel Works
- a flat plate test body (400 mm ⁇ 200 mm ⁇ 3 mm thickness) was prepared from the obtained pellets using an injection molding machine (S-2000i100B manufactured by FUNAC, cylinder diameter 27 mm), and the surface resistance value and the volume resistance value were measured.
- Reference Example 2 and Example 1 The same operation as in Reference Example 1 was conducted except that the amount of carbon nanotube added was 1.5 and 2.0 parts by mass. The evaluation results are shown in Table 1.
- Comparative Example 1 was carried out in the same manner as Reference Example 1 except that the application was performed without applying a voltage to the electrostatic automatic gun during the coating of natural ABS resin (without filler). The evaluation results are shown in Table 1. Comparative Example 2 was carried out in the same manner as Reference Example 1 except that a conductive primer was applied to the natural ABS resin. The evaluation results are shown in Table 1.
- the resistance and coating efficiency of the results of the above examples and comparative examples are shown in FIG. As can be seen from the figure, the coating efficiency is excellent by adjusting the surface resistance value (corresponding to the resistance of the skin layer) and the volume resistance value (corresponding to the resistance of the core layer) to a predetermined range.
- Examples 2 and 3 100 parts by mass of ABS resin and 2.0 parts by mass of carbon nanotubes (Example 2) or 1.5 parts by mass (Example 3) are fed from the main feed port of the same-direction twin-screw extruder (KZW15TW, manufactured by Technobel Co., Ltd.). did.
- the temperatures of the six barrels of the extruder are 220 ° C, 230 ° C, 240 ° C, 250 ° C, 250 ° C, 250 ° C in the direction of extrusion, and the nozzle head temperature is set to 250 ° C.
- the mixture was melt-kneaded under the conditions of a screw rotation speed of 600 rpm and a discharge amount of 2 kg / h, cut with a pelletizer and processed into a pellet.
- the screw elements of the same direction twin screw extruder were provided with kneading disks at a total of three locations so that the carbon nanotubes were uniformly dispersed in the molten resin.
- the obtained pellets were molded by an injection molding machine (Nissei Resin Co., Ltd. FNX140, cylinder diameter 40 mm) to obtain a flat plate test body (350 mm ⁇ 100 mm ⁇ 2 mm thickness), which was subjected to physical property measurement.
- the molding conditions are a mold temperature of 60 ° C., a cylinder temperature of 260 ° C., and an injection speed of 5 mm / s.
- the cylinder temperature was set higher than 220 to 230 ° C., which is the recommended molding temperature for ABS resin.
- Various physical properties were measured, the coating efficiency was evaluated, and the results are shown in Table 2.
- Example 4 The operation was performed in the same manner as in Example 2 except that the injection speed was 10 mm / s. The evaluation results are shown in Table 2.
- Comparative Examples 3 and 4 The carbon nanotubes were added in amounts of 1.5 parts by mass (Comparative Example 3) and 1.0 part by mass (Comparative Example 4), and molded by an injection molding machine (FUNAC S-2000i100B, cylinder diameter 27 mm), 400 mm ⁇ 200 mm. A flat plate test piece having a thickness of 3 mm was obtained. The mold temperature is 60 ° C., the cylinder temperature is 260 ° C., and the injection speed is 10 mm / s. The other operations were performed in the same manner as in Example 2. The evaluation results are shown in Table 2.
- Comparative Example 5 ABS resin was molded by an injection molding machine (FUNAC S-2000i100B, cylinder diameter 27 mm) to obtain a flat plate test piece of 400 mm ⁇ 200 mm ⁇ 3 mm thickness. The operation was performed in the same manner as in Example 2 except that the test piece was coated without applying a voltage to the electrostatic automatic gun. The evaluation results are shown in Table 2.
- ABS resin was molded by an injection molding machine (FUNAC S-2000i100B, cylinder diameter 27 mm) to obtain a flat plate test piece of 400 mm ⁇ 200 mm ⁇ 3 mm thickness.
- a conductive primer (Primac No. 1700 conductive primer, manufactured by BASF Coatings) containing 1 to 5 parts by mass of carbon black was applied to the test piece and dried to prepare a test piece. The test piece was evaluated in the same manner as in Example 2, and the results are shown in Table 2.
- the coating efficiency is 1 or more, and it is possible to obtain characteristics equal to or higher than the coating efficiency when the conductive primer is used.
Abstract
Description
(2)表面抵抗値1.0×103Ω/□以上、9.9×1013Ω/□以下、体積抵抗値1.0×103Ω・cm以上、9.9×105Ω・cm以下である(1)に記載の静電塗装用樹脂成形体。
(3)静電塗装用樹脂成形体は、炭素材料と熱可塑性樹脂の混合物を含む(1)または(2)に記載の塗装用樹脂成形体。
(4)炭素材料が炭素繊維である(3)に記載の塗装用樹脂成形体。
(5)炭素繊維がカーボンナノチューブである(4)に記載の塗装用樹脂成形体。
(6)熱可塑性樹脂がABS樹脂、AES樹脂、ASA樹脂、AS樹脂、HIPS樹脂、スチレン・アクリロニトリル共重合体、ポリエチレン、ポリプロピレン、ポリカーボネート(PC)、ポリカーボネートとABSのアロイ(PC/ABS)、ポリフェニレンエーテル(PPE)、ポリアミド(PA)から選ばれる少なくとも1種を含有する、(3)~(5)のいずれかに記載の塗装用樹脂成形体。
(7)熱可塑性樹脂100質量部に対し、炭素材料の含有量が0.5~10質量部である(3)~(6)のいずれかに記載の塗装用樹脂成形体。
(8)表面抵抗値9.9×1013Ω/□以下、体積抵抗値9.9×105Ω・cm以下である静電塗装用樹脂成形体に、電荷を有する塗料を吹き付けることを特徴とする樹脂成形体の静電塗装方法。
(9)表面抵抗値9.9×1013Ω/□以下、体積抵抗値9.9×105Ω・cm以下である静電塗装用樹脂成形体に、電荷を有する塗料を吹き付けることを特徴とする塗膜を有する樹脂成形体の製造方法。
(10)表面抵抗値9.9×1013Ω/□以下、体積抵抗値9.9×105Ω・cm以下である静電塗装用樹脂成形体に、電荷を有する塗料を吹き付けることを特徴とする塗膜を有する車両用部品の製造方法。
樹脂を成形する場合には、表面と中心部に不均一性が生じることが知られている。たとえば、熱可塑性樹脂成形体は熱により溶融された樹脂が低温の金型キャビティ内に充填され、冷却固化され得られるが、その際には、冷却速度の違いにより、樹脂流れが異なる層ができることで配向し、流れに対して垂直方向にスキン層とコア層ができる。
スキン層とは、得られた成形体の表面から厚さ方向に約200μmまでをいい、コア層とは約200μm以上の深さの部分をいう。
このように、表面抵抗が大きな材料であっても、体積抵抗を所定の範囲に設定することにより、良好な塗着効率を発現できる。そのため添加する導電性フィラーの量を低減することができ、よって成形体の機械的物性等の低下を抑制できる。なお、体積抵抗値が所定の範囲であっても、表面抵抗値が大きすぎると塗着効率が低下する。
本明細書において表面抵抗及び体積抵抗は実施例に記載の方法により測定することができる。
本発明で用いる樹脂は特に限定されないが、衝撃特性、流動性が高い樹脂を用いるのが好ましい。
衝撃特性が高い樹脂としては、IZOD衝撃強度が200J/m以上である熱可塑性樹脂が挙げられる。流動特性が高い樹脂としては、メルトフローレート10~30g/10min.(220℃、10kgf荷重)である熱可塑性樹脂が挙げられる。
ポリスチレン、スチレン-アクリロニトリル共重合体、スチレン-無水マレイン酸共重合体、(メタ)アクリル酸エステル-スチレン共重合体等のスチレン系(共)重合体;
ABS(アクリロニトリル-ブタジエン-スチレン)樹脂、AES(アクリロニトリル-エチレン(EPDM)-スチレン)樹脂、ASA(アクリロニトリル-スチレン-アクリレート)樹脂、HIPS(耐衝撃性ポリスチレン)樹脂等のゴム強化樹脂;
ポリエチレン、ポリプロピレン、エチレン-プロピレン共重合体等の、炭素数2~10のα-オレフィンの少なくとも1種をモノマーとするα-オレフィン(共)重合体及びその変性重合体(塩素化ポリエチレン等)、並びに環状オレフィン共重合体等のオレフィン系樹脂;
アイオノマー、エチレン-酢酸ビニル共重合体、エチレン-ビニルアルコール共重合体等のエチレン系共重合体;
ポリ塩化ビニル、エチレン-塩化ビニル重合体、ポリ塩化ビニリデン等の塩化ビニル系樹脂;
ポリメタクリル酸メチル(PMMA)等の(メタ)アクリル酸エステルの1種以上をモノマーとする(共)重合体からなるアクリル系樹脂;
ポリアミド6、ポリアミド66、ポリアミド612等のポリアミド系樹脂(PA);
ポリカーボネート(PC);
ポリエチレンテレフタレート(PET)、ポリブチレンフタレート(PBT)、ポリエチレンナフタレート等のポリエステル系樹脂;
ポリアセタール樹脂(POM);
ポリフェニレンエーテル(PPE);
ポリアリレート樹脂;
ポリテトラフルオロエチレン、ポリフッ化ビニリデン等のフッ素樹脂;
液晶ポリエステルといった液晶ポリマー;
ポリイミド、ポリアミドイミド、ポリエーテルイミド等のイミド樹脂;
ポリエーテルケトン等のケトン系樹脂;
ポリスルホン、ポリエーテルスルホン等のスルホン系樹脂;
ウレタン系樹脂;
ポリ酢酸ビニル;
ポリエチレンオキシド;
ポリビニルアルコール;
ポリビニルエーテル;
ポリビニルブチラート;
フェノキシ樹脂;
感光性樹脂;
生分解性プラスチック等があげられる。
樹脂に添加する炭素材料は特に限定されないが、たとえば炭素繊維を使用することができる。炭素繊維として、ピッチ系炭素繊維、PAN系炭素繊維、カーボンファイバー、カーボンナノファイバー、カーボンナノチューブ等が使用可能であるが、添加量を少なくするという観点からは、カーボンナノチューブを使用することが好ましい。好ましい態様のカーボンナノチューブは、繊維の中心部に空洞を有するチューブ状であり、グラフェン面が繊維軸に対して略平行に伸長している。なお、本発明において、略平行とは、繊維軸に対するグラフェン層の傾きが約±15度以内のことをいう。空洞部分は繊維長手方向に連続していてもよいし、不連続になっていてもよい。
炭素繊維のR値は、0.1以上が好ましく、0.2~2.0がより好ましく、0.5~1.5がさらに好ましい。なお、R値は大きいほど結晶性が低いことを示す。
炭素繊維を分散させた静電塗装用樹脂成形体を構成する各成分を混合・混練する際には、炭素繊維の破断を極力抑えるように行うことが好ましい。具体的には、炭素繊維の破断率を20%以下に抑えることが好ましく、15%以下に抑えることが更に好ましく、10%以下に抑えることが特に好ましい。破断率は、混合・混練の前後での炭素繊維のアスペクト比(例えば、電子顕微鏡SEM観察により測定)を比較することにより評価する。炭素繊維の破断を極力抑えて混合・混練するには、例えば、以下のような手法を用いることができる。
前記ニーディングディスクについては、同方向2軸押出機における炭素繊維の分散性を考慮して使用することもできる。ニーディングディスクを用いることができる。
溶融混練する際の温度、吐出量、混練時間などの条件は、混練機器の種類、能力、静電塗装用樹脂成形体を構成する各成分の性質、割合などに応じて適宜選定し決定することができる。
これらの組成物から成形品を製造する際には、従来から知られている樹脂組成物の成形法によることができる。成形法としては、例えば、射出成形法、中空成形法、押出成形法、シート成形法、熱成形法、回転成形法、積層成形法、トランスファー成形法などが挙げられる。好ましくは射出成形法である。
成形温度は、通常の熱可塑性樹脂の射出成形に用いられる温度よりも高く設定する。具体的には、使用する樹脂にて推奨されている射出成形温度よりも、10~60℃高い温度で射出成形を行う。例えば、本実施例で用いたABS樹脂については、サプライヤーが示す樹脂の推奨成形温度は220~230℃であるが、本発明の好ましい実施態様においては射出成形は好ましくは230℃~290℃、より好ましくは240℃~270℃で行う。射出成形温度が低い場合、射出時に溶融樹脂にはせん断力が生じ易くなり、特にスキン層に過度のせん断力が生じ、炭素繊維が樹脂の流動方向に配向し抵抗値が高くなる。射出成形温度を高くすることにより、射出時の溶融樹脂にせん断力が生じ難く、炭素繊維がランダムに分散し、炭素繊維同士の導電パスが生じ易く、抵抗値が低くなる。
また、射出速度は低速度が好ましく、成形品の表面外観や寸法精度を損なわない最低速度で行う。射出速度が高速であると溶融樹脂には過度のせん断力が生じ易くなり、特にスキン層に過度のせん断力が生じ、炭素繊維が樹脂の流動方向に配向し抵抗値が高くなる。射出速度を低くすることにより、射出時の溶融樹脂にせん断力が生じ難く、炭素繊維がランダムに分散し、カーボンナノチューブ同士の導電パスが生じ易く、抵抗値が低くなる。
温度および射出速度を調整することにより、導電性フィラーのネットワークによりスキン層とコア層との導電パスが生じ、同じ抵抗値を有する成形体と比較しても、塗着効率に優れたものが得られる。
以上において説明した静電塗装用樹脂成形体は、耐衝撃性とともに塗装が要求される製品や部品、例えばOA機器、電子機器に使用される部品、自動車部品などの車両用部品の塗装に好適に使用できる。
なお、各例にて使用した成分および物性評価方法は以下の通りである。
使用成分の内訳は以下の通りである。
・熱可塑性樹脂:ABS樹脂(東レ株式会社製トヨラック100-MPM,メルトフローレート(220℃,10kgf荷重):15g/10分),
・カーボンナノチューブ:昭和電工株式会社製VGCF(登録商標)-X,平均繊維径15nm,平均繊維長3μm,BET比表面積260m2/g。
成形体より100mm×100mm(厚みは成形体の厚み)のサイズの試験片を切り出し、JIS K6911に準拠して、2重リング電極法にて表面抵抗値を測定した。100Vを電極間に印加し、1分後の抵抗値を測定した。
成形体より60mm×10mm(厚みは成形体の厚み)のサイズの試験片を切り出し、長手方向の断面に導電テープを張り、切断面間の電気抵抗値を測定した。抵抗値は、デジタル式絶縁抵抗機(MY40、YOKOGAWA社製)を用い、加電圧500Vにて測定した。体積抵抗値は、次式により算出した。
体積抵抗値[Ω・cm]=抵抗値[Ω]×断面積[cm2]/試験片長さ[cm]
ISO1133に準拠して、試験温度220℃、試験荷重10kgfにて測定した。
ASTMD256に準拠し、アイゾット衝撃試験片(ノッチ付)を作製し評価した。
ユアサアイオニクス製NOVA1000を用いて液体窒素温度下(77K)において窒素ガスを吸着させるBET法により計測した。
小型ロボットにエア霧化静電自動ガンを装着し、ギアポンプにて塗料の供給を行い、平置きした試験平板に電圧を印加し静電塗装した。塗装工程としては、下塗り(カラー)塗装後に乾燥して質量測定を行い、その後上塗り(クリアー)塗装後に乾燥して質量測定を行った。乾燥条件は80℃で20分間保持である。各塗膜厚みの設定は下塗り20μm、上塗り30μmとした。各塗料の付着量は事前に測定した試験平板の質量と、各乾燥後の質量との差から算出した。この付着量から塗着効率を算出した。塗着効率比は比較例4(導電プライマーを使用した場合)の塗着効率を1とし、比を算出した。
同方向2軸押出機(TEX30α日本製鋼所(株)製)の主フィード口からABS樹脂100質量部とカーボンナノチューブ1質量部を投入し、混練された樹脂組成物はペレタイザで切断しペレット状に加工した。
カーボンナノチューブの添加量を1.5および2.0質量部にした以外は、参考例1と同様に実施した。評価結果を表1に示す。
比較例2はABS樹脂のナチュラルに導電プライマーを塗布した以外は、参考例1と同様に実施した。評価結果を表1に示す。
同方向2軸押出機(KZW15TW、株式会社テクノベル製)の主フィード口からABS樹脂100質量部とカーボンナノチューブ2.0質量部(実施例2)または1.5質量部(実施例3)を投入した。押出機の6個のバレルの温度(加熱ゾーンの温度)は押出方向に向かって220℃、230℃、240℃、250℃、250℃、250℃とし、ノズルヘッドの温度は250℃に設定し、スクリュー回転数を600rpm、吐出量を2kg/hとの条件で溶融混練し、ペレタイザで切断しペレット状に加工した。同方向2軸押出機のスクリューエレメントはカーボンナノチューブが溶融樹脂に均一に分散されるように、計3箇所にニーディングディスクを配設した。
得られたペレットを、射出成形機(日精樹脂工業社製FNX140,シリンダー径40mm)により成形し平板試験体(350mm×100mm×2mm厚)を得、物性測定に供した。成形条件は、金型温度60℃、シリンダ温度260℃、射出速度5mm/sである。このシリンダ温度は、ABS樹脂の推奨成形温度である220~230℃よりも高く設定した。
各種物性を測定し、塗着効率を評価し、結果を表2に示した。
射出速度を10mm/sにした以外は、実施例2と同様に操作を行った。評価結果を表2に示す。
カーボンナノチューブの添加量を1.5質量部(比較例3)および1.0質量部(比較例4)にし、射出成形機(FUNAC製S-2000i100B,シリンダー径27mm)により成形し、400mm×200mm×3mm厚の平板試験片を得た。金型温度60℃、シリンダ温度260℃、射出速度10mm/sである。その他は、実施例2と同様に操作を行った。評価結果を表2に示す。
ABS樹脂を射出成形機(FUNAC製S-2000i100B,シリンダー径27mm)により成形し、400mm×200mm×3mm厚の平板試験片を得た。その試験片を静電自動ガンに電圧を印加せずに塗装を行った以外は、実施例2と同様に操作を行った。評価結果を表2に示す。
ABS樹脂を射出成形機(FUNAC製S-2000i100B,シリンダー径27mm)により成形し、400mm×200mm×3mm厚の平板試験片を得た。その試験片にカーボンブラック1~5質量部含有した導電プライマー(プライマックNo.1700導電プライマー、BASFコーティングス(株)製)を塗布し乾燥し試験片を調製した。その試験片について、実施例2と同様に評価を行い、結果を表2に示す。
Claims (7)
- 平均繊維径が1nm以上150nm以下の炭素繊維及び樹脂を含み、表面抵抗値が1.0×103Ω/□以上、9.9×1013Ω/□以下、体積抵抗値が1.0×103Ω・cm以上、9.9×105Ω・cm以下である静電塗装用樹脂成形体。
- 前記表面抵抗値が1.0×103Ω/□以上、9.9×1012Ω/□以下であり、前記体積抵抗値が1.0×103Ω・cm以上、1.0×105Ω・cm以下である請求項1に記載の静電塗装用樹脂成形体。
- 前記樹脂が、ABS樹脂、AES樹脂、ASA樹脂、AS樹脂、HIPS樹脂、スチレン・アクリロニトリル共重合体、ポリエチレン、ポリプロピレン、ポリカーボネート(PC)、ポリカーボネートとABSのアロイ(PC/ABS)、ポリフェニレンエーテル(PPE)、ポリアミド(PA)から選ばれる熱可塑性樹脂を少なくとも1種含有する請求項1に記載の静電塗装用樹脂成形体。
- 前記樹脂を100質量部とした場合、前記炭素繊維の含有量が0.5~10質量部である請求項1に記載の静電塗装用樹脂成形体。
- 請求項1に記載の静電塗装用樹脂成形体に電荷を有する塗料を吹き付ける工程を有することを特徴とする樹脂成形体の静電塗装方法。
- 請求項1に記載の静電塗装用樹脂成形体に電荷を有する塗料を吹き付ける工程を有することを特徴とする、塗膜を有する樹脂成形体の製造方法。
- 請求項1に記載の静電塗装用樹脂成形体に電荷を有する塗料を吹き付ける工程を有することを特徴とする、塗膜を有する車両用部品の製造方法。
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JP2718957B2 (ja) * | 1988-10-05 | 1998-02-25 | ポリプラスチックス株式会社 | 結晶性熱可塑性樹脂成形品の静電塗装方法並びに塗装プラスチックス成形品 |
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2012
- 2012-12-20 KR KR1020147009543A patent/KR20140063791A/ko not_active Application Discontinuation
- 2012-12-20 TW TW101148764A patent/TW201341444A/zh unknown
- 2012-12-20 WO PCT/JP2012/083077 patent/WO2013094686A1/ja active Application Filing
- 2012-12-20 JP JP2013550332A patent/JPWO2013094686A1/ja active Pending
- 2012-12-20 US US14/367,027 patent/US20140356544A1/en not_active Abandoned
- 2012-12-20 BR BR112014014623A patent/BR112014014623A2/pt not_active Application Discontinuation
- 2012-12-20 AU AU2012354715A patent/AU2012354715A1/en not_active Abandoned
- 2012-12-20 CN CN201280063619.6A patent/CN104011141A/zh active Pending
Patent Citations (4)
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JPH0848869A (ja) * | 1994-06-01 | 1996-02-20 | General Electric Co <Ge> | 相溶化されたポリフェニレンエーテル‐ポリアミドベース樹脂および導電性のカーボンブラックを含む熱可塑性組成物 |
JP2001098092A (ja) * | 1999-07-23 | 2001-04-10 | Osaka Gas Co Ltd | 被静電塗装用樹脂成形体およびその製造方法 |
JP2008274060A (ja) * | 2007-04-27 | 2008-11-13 | Nano Carbon Technologies Kk | 樹脂材料と導電性フィラーとの混合方法及び該方法により作製された複合材料及びマスターペレット |
JP2009280825A (ja) * | 2009-07-16 | 2009-12-03 | Mitsubishi Engineering Plastics Corp | 熱可塑性樹脂組成物及びその成形体 |
Also Published As
Publication number | Publication date |
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KR20140063791A (ko) | 2014-05-27 |
AU2012354715A1 (en) | 2014-07-24 |
JPWO2013094686A1 (ja) | 2015-04-27 |
BR112014014623A2 (pt) | 2017-06-13 |
TW201341444A (zh) | 2013-10-16 |
CN104011141A (zh) | 2014-08-27 |
US20140356544A1 (en) | 2014-12-04 |
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